CN116404150A - Double-anion sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Double-anion sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116404150A CN116404150A CN202310440725.1A CN202310440725A CN116404150A CN 116404150 A CN116404150 A CN 116404150A CN 202310440725 A CN202310440725 A CN 202310440725A CN 116404150 A CN116404150 A CN 116404150A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 60
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 150000001450 anions Chemical class 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a double-anion sodium ion battery anode material and a preparation method and application thereof, and belongs to the technical field of sodium ion batteries. The positive electrode material of the dianion sodium ion battery comprises at least one compound of the formula Na p Cu x Fe y Mn z M q O (2‑α‑β) (SO 4 ) β F α Wherein M is a doping element other than Cu, fe, mn; p is more than 0.61 and less than or equal to 0.78,0.22, x is more than or equal to 0.33,0.10, y is more than or equal to 0.12,0.45, z is more than or equal to 0.78,0.08, q is more than or equal to 0.12, and x+y+z+q=1; alpha is more than 0 and less than or equal to0.1; beta is more than 0 and less than or equal to 0.05, and the values of p, x, y, z, q, alpha and beta meet the charge balance of chemical formulas. The positive electrode material of the dianion sodium ion battery provided by the invention takes sulfate radical and fluoride ion as anions, and the two anions have stronger electronegativity and form a more stable structure with cations in the material, so that the free distance of sodium ions is shortened, and the structural stability is improved.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a dianion sodium ion battery anode material and a preparation method and application thereof.
Background
With the progress of human society, the demand for energy is also increasing with the development of technology. Fossil energy plays a great role therein, but is more polluted. From the end of the last century, people have gradually put their eyes on clean energy, and the solar energy, wind energy, tidal energy, nuclear energy, etc. have gradually increased in the use of energy. Meanwhile, the battery industry is continuously improved, from alkaline batteries to lead-acid batteries to lithium ion batteries, the battery energy density is higher and higher, the performance is better, and the battery is more friendly to the environment.
At present, a plurality of lithium ion batteries are on the market, and have excellent performance, but the defects are obvious. Firstly, the content of lithium element in crust is lower, which is only 0.0065%. Secondly, lithium ores are intensively distributed in south america, most of China relies on import, which is unfavorable for developing lithium resource industry on one hand and is easy to be restricted by people in international situation on the other hand. Under such circumstances, a material capable of replacing a lithium ion battery is urgently needed. Sodium ion batteries have been studied in the last century, and sodium resources are widely distributed and stored quite much, but are put aside due to the problems of low energy density, unstable structure and the like.
The sodium ion battery mainly comprises a sodium ion battery anode material, and materials such as layered oxide, polyanion compound, prussian blue and the like are researched in recent years, wherein the layered oxide is emphasized and researched due to higher energy density and relatively simple process, and is suitable for industrialization. However, the problem of poor circulation is difficult to solve because the layered oxide structure is unstable, and the practical application still has great difficulty. Generally, there are two modification methods, doping and cladding, respectively, in which the doping element enters the bulk phase, and replaces some elements on the lattice, thus impeding structural distortion. The coating element is arranged on the surface of the material to isolate the contact of the positive electrode material with air, water and electrolyte, thereby effectively inhibiting the cycle deterioration. Both methods have a certain effect on the lifting performance, but still have a larger lifting space. By introducing anions, the conductivity is improved, the polarization voltage is reduced, the impurity phase is removed, the irreversible phase change is inhibited, and the structural stability is improved.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of poor cycling stability and the like of the layered oxide sodium ion battery anode material in the prior art.
In order to solve the technical problems, the invention provides a dianion sodium ion battery anode material and a preparation method and application thereof.
A first object of the present invention is to provide a dianion sodium-ion battery positive electrode material comprising at least one compound having the formula Na p Cu x Fe y Mn z M q O (2-α-β) (SO 4 ) β F α Wherein M is a doping element other than Cu, fe, mn; p is more than 0.61 and less than or equal to 0.78,0.22, x is more than or equal to 0.33,0.10, y is more than or equal to 0.12,0.45, z is more than or equal to 0.78,0.08, q is more than or equal to 0.12, and x+y+z+q=1; alpha is more than 0 and less than or equal to 0.1; beta is more than 0 and less than or equal to 0.05, and the values of p, x, y, z, q, alpha and beta meet the charge balance of chemical formulas.
In one embodiment of the invention, the M is selected from one or more of Mg, ca, sr, sn, zn, Y, nb, sb, bi, cd, mo, cr and Co.
The second object of the invention is to provide a method for preparing the positive electrode material of the dianion sodium ion battery, which comprises the following steps,
(1) Uniformly mixing a copper source, an iron source, a manganese source and an M source, and performing ball milling and calcination to obtain an M doped precursor;
(2) And (3) uniformly mixing the M doped precursor in the step (1) with a sulfuric acid source, a fluorine source and a sodium source, ball milling and calcining to obtain the dianion sodium ion battery anode material.
In one embodiment of the present invention, in step (1), the copper source, the iron source, and the manganese source are independently selected from one or more of oxides, carbonates, acetates, and hydroxides of the corresponding elements;
the M source is selected from one or more of oxides, carbonates, fluorides, hydroxides, acetates and sulfates.
In one embodiment of the invention, in step (1), the calcination is carried out at a temperature of 350 ℃ to 500 ℃ for a time of 3h to 6h.
In one embodiment of the invention, in the step (1), the ball milling time is 8-12 h, the rotating speed is 400-600 r/min, and the ball ratio is 10 g/ball.
In one embodiment of the invention, in step (2), the sulfuric acid source is selected from one or more of sodium sulfate, magnesium sulfate, zinc sulfate, aluminum sulfate, and calcium sulfate;
the fluorine source is selected from one or more of sodium fluoride, magnesium fluoride, calcium fluoride and aluminum fluoride;
the sodium source is selected from one or more of sodium fluoride, sodium carbonate, sodium hydroxide, sodium oxalate and sodium sulfate.
In one embodiment of the invention, in step (2), the calcination is performed at a temperature of 950 ℃ to 1050 ℃ for a time of 8 hours to 12 hours.
In one embodiment of the invention, in the step (2), the ball milling time is 3-5 h, the rotating speed is 200-400 r/min, and the ball ratio is 10 g/ball.
The third object of the invention is to provide a positive electrode of a sodium ion battery, which comprises the positive electrode material of the dianion sodium ion battery, a conductive agent and a binder in parts by mass; the consumption of the conductive agent is less than or equal to 10wt%; the usage amount of the binder is less than or equal to 10wt%.
Further, the conductive agent is used in an amount of 0.01w% t-10wt%,1wt% -10wt%,2wt% -10wt%,3wt% -10wt%,4wt% -10wt%,5wt% -10wt%,6wt% -10wt%,7wt% -10wt%,8wt% -10wt%, and 9wt% -10wt%.0.01wt%, 0.05wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%; or any concentration value between any two values.
Further, the binder is used in an amount of 0.01w% t-10wt%,1wt% -10wt%,2wt% -10wt%,3wt% -10wt%,4wt% -10wt%,5wt% -10wt%,6wt% -10wt%,7wt% -10wt%,8wt% -10wt%, and 9wt% -10wt%.0.01wt%, 0.05wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%; or any concentration value between any two values.
In one embodiment of the present invention, the conductive agent is selected from one or more of carbon nanotubes, acetylene black, conductive carbon black, conductive graphite, carbon fibers, and graphene;
the binder is selected from one or more of polyolefin, fluorine-containing resin, polypropylene resin and rubber.
Further, the binder is selected from one or more of polyvinylidene fluoride, benzene rubber, nitrile rubber, styrene Butadiene Rubber (SBR), polyacrylamide (PAA), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), polyimide (PI), butadiene rubber, modified butadiene rubber, carboxyl modified styrene butadiene rubber, and modified polyorganosiloxane-based polymer.
A fourth object of the present invention is to provide a sodium ion battery comprising the positive electrode of the sodium ion battery.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The positive electrode material of the dianion sodium ion battery improves conductivity by utilizing fluoride ions, reduces polarization voltage, removes impurity phases and improves structural stability. On the other hand, fluorine ions and oxygen are combined to form a stable covalent bond, unfavorable P2-O2 phase change is inhibited, the structure is maintained stable, and the capacity retention rate is effectively improved.
(2) The positive electrode material of the dianion sodium ion battery provided by the invention takes sulfate radical as an anion, the sulfate radical is subjected to sp3 hybridization, and the existing structure is more stable.
(3) The positive electrode material of the dianion sodium ion battery provided by the invention takes sulfate radical and fluoride ion as anions, and the two anions have stronger electronegativity and form a more stable structure with cations in the material, so that the free distance of sodium ions is shortened, and the structural stability is improved.
(4) The positive electrode material of the dianion sodium ion battery has excellent multiplying power performance, good cycle performance and relatively simple manufacture, and is suitable for industrial production.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
fig. 1 is an XRD comparison pattern of the positive electrode materials of sodium ion batteries of example 1 and comparative example 1 of the present invention.
Fig. 2 is a graph showing the pH change with time of the positive electrode materials for sodium ion batteries of example 1 and comparative example 1 of the present invention.
Fig. 3 is a graph showing the cycle performance of the positive electrode materials for sodium ion batteries of example 1 and comparative example 1 according to the present invention.
Fig. 4 is a graph showing the cycle performance of the positive electrode materials for sodium ion batteries of example 2 and comparative example 2 according to the present invention.
Fig. 5 is a graph showing the cycle performance of the positive electrode materials for sodium ion batteries of example 3 and comparative example 3 according to the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, the ball ratio during ball milling in examples was 10 g/ball unless otherwise specified.
Example 1
A double-anion sodium ion battery anode material and a preparation method thereof specifically comprise the following steps:
39.773g of copper oxide (CuO) and 99.108g of manganese dioxide (MnO) were weighed 2 ) 31.938g of ferric oxide (Fe 2 O 3 ) 13.025g of zinc oxide (ZnO) is placed in a ball milling tank, the ball milling speed is 600r/min, the mixture is mixed for 10 hours at high speed, then calcined for 6 hours at 500 ℃, and after cooling and sieving, the Zn-doped copper-iron-manganese precursor is obtained.
90.017g of a Zn-doped copper-iron-manganese precursor, 35.506g of sodium carbonate (Na 2 CO 3 ) 1.421g of sodium sulfate (Na 2 SO 4) and 0.420g of sodium fluoride (NaF), placing the materials into a ball milling tank, mixing the materials at a high speed of 300r/min for 3 hours, calcining the materials at 1020 ℃ for 9 hours, cooling and sieving the materials, and finally obtaining the positive electrode material of the dianion sodium ion battery with stable structure.
Example 2
A double-anion sodium ion battery anode material and a preparation method thereof specifically comprise the following steps:
39.733g of copper oxide (CuO) and 95.631g of manganese dioxide (MnO) were weighed 2 ) 31.938g of ferric oxide (Fe 2 O 3 ) 16.282g of zinc oxide (ZnO) is placed in a ball milling tank, the ball milling speed is 500r/min, the mixture is mixed for 8 hours at high speed, then the mixture is calcined for 4 hours at 500 ℃, and after cooling and sieving, the Zn-doped copper-iron-manganese precursor is obtained.
90.227g of a Zn-doped copper-iron-manganese precursor, 35.506g of sodium carbonate (Na 2 CO 3 ) 2.842g sodium sulfate (Na 2 SO 4 ) And (3) 0.820g of sodium fluoride (NaF) is placed in a ball milling tank, the ball milling speed is 300r/min, the high-speed mixing is carried out for 3 hours, the calcination is carried out for 10 hours at 1000 ℃, and after cooling and sieving, the double-anion sodium ion battery anode material with stable structure is finally obtained.
Example 3
A double-anion sodium ion battery anode material and a preparation method thereof specifically comprise the following steps:
42.955g of copper oxide (CuO) and 90.414g of manganese dioxide (MnO) were weighed 2 ) 35.132g of ferric oxide (Fe 2 O 3 ) 8.061g of magnesium oxide (MgO) is placed in a ball milling pot, the ball milling speed is 450r/min, the mixture is mixed for 10 hours at high speed, then calcined for 6 hours at 480 ℃, and after cooling and sieving, the Mg-doped copper-iron-manganese precursor is obtained.
86.298g of Mg-doped copper-iron-manganese precursor, 35.506g of sodium carbonate (Na 2 CO 3 ) 1.204g of magnesium sulfate (MgSO 4 ) 0.781g of calcium fluoride (CaF) 2 ) Placing the materials in a ball milling tank, mixing the materials at a high speed for 3 hours at a rotating speed of 300r/min, calcining the materials at 980 ℃ for 12 hours, cooling and sieving the materials, and finally obtaining the positive electrode material of the dianion sodium ion battery with stable structure.
Example 4
A double-anion sodium ion battery anode material and a preparation method thereof specifically comprise the following steps:
42.955g of copper oxide (CuO) and 90.414g of manganese dioxide (MnO) were weighed 2 ) 35.132g of ferric oxide (Fe 2 O 3 ) 30.142g tin oxide (SnO) 2 ) Placing the mixture into a ball milling tank, mixing the mixture at a high speed for 8 hours at a rotating speed of 500r/min, calcining the mixture at a temperature of 500 ℃ for 6 hours, and cooling and sieving the mixture to obtain the Sn-doped copper-iron-manganese precursor.
95.738g of Sn-doped copper-iron-manganese precursor, 35.506g of sodium carbonate (Na 2 CO 3 ) 1.421g of sodium sulfate (Na 2 SO 4 ) 0.781g of calcium fluoride (CaF) 2 ) Placing the materials in a ball milling tank, mixing the materials at a high speed for 3 hours at a rotating speed of 300r/min, calcining the materials at 980 ℃ for 12 hours, cooling and sieving the materials, and finally obtaining the positive electrode material of the dianion sodium ion battery with stable structure.
Comparative example 1
19.887g of copper oxide (CuO) and 49.553g of manganese dioxide (MnO) were weighed 2 ) 15.970g of ferric oxide (Fe 2 O 3 ) 6.513g of zinc oxide (ZnO), 35.506g of sodium carbonate (Na 2 CO 3 ) Placing the mixture into a ball milling tank, mixing the mixture at a high speed for 3 hours at a rotating speed of 300r/min, calcining the mixture at 1020 ℃ for 9 hours, cooling and sieving the mixture, and finally obtaining the sodium ion battery anode material.
Comparative example 2
19.887g of copper oxide (CuO) and 49.553g of manganese dioxide (MnO) were weighed 2 ) 15.970g of ferric oxide (Fe 2 O 3 ) 8.141g of zinc oxide (ZnO), 35.506g of sodium carbonate (Na 2 CO 3 ) Placing the mixture into a ball milling tank, mixing the mixture at a high speed for 3 hours at a rotating speed of 300r/min, calcining the mixture at 1000 ℃ for 10 hours, cooling and sieving the mixture, and finally obtaining the sodium ion battery anode material.
Comparative example 3
19.887g of copper oxide (CuO) and 49.553g of manganese dioxide (MnO) were weighed 2 ) 15.970g of ferric oxide (Fe 2 O 3 ) 4.031g of magnesium oxide (MgO), 35.132g of sodium carbonate (Na 2 CO 3 ) Placing the mixture into a ball milling tank, mixing the mixture at a high speed for 3 hours at a rotating speed of 300r/min, calcining the mixture at 1000 ℃ for 10 hours, cooling and sieving the mixture, and finally obtaining the sodium ion battery anode material.
Test example 1
XRD analysis was performed on the positive electrode materials for sodium-ion batteries prepared in example 1 and comparative example 1, and as shown in fig. 1, it can be seen from fig. 1 that the positive electrode materials for sodium-ion batteries prepared in example 1 and comparative example 1 each have a P2 type structure in the main structure.
Test example 2
The positive electrode materials for sodium ion batteries prepared in example 1 and comparative example 1 were subjected to pH test after being exposed to air for 5, 9, 13, 17, 21 days, and the results are shown in FIG. 2. As can be seen from FIG. 2, the pH value of example 2 is less varied with time, and the rate of pH increase is significantly smaller than that of comparative example 2 because of SO 4 2- Has strong attraction to cations, inhibits precipitation of sodium ions, reduces absorption of water in air, and thus causes less pH value change.
Test example 3
In an environment with 50% of air humidity, the positive electrode materials of the sodium ion batteries obtained in examples 1-3 and comparative examples 1-3 are used for preparing a button cell for testing electrical performance, wherein the weight ratio of electrode components is as follows: conductive agent (acetylene black): binder (PVDF) =80: 10:10; the negative electrode adopts sodium sheet, and the cycle performance of the button cell is shown in figures 3-5. It can be seen from FIGS. 3-5 that the cycle of examples 1-3 is superior to comparative examples 1-3, doped with SO 4 2- After that, S occupies part of transition metal position, SO 4 2- S performs sp3 hybridization, is relatively stable and plays an important role in structure stability. F (F) - The doping replaces part of oxygen positions in the structure, forms a stable covalent bond with oxygen, inhibits unfavorable P2-O2 phase change, and improves the circulation stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The dianion sodium ion battery positive electrode material is characterized by comprising at least one compound of the formula Na p Cu x Fe y Mn z M q O (2-α-β) (SO 4 ) β F α Wherein M is a doping element other than Cu, fe, mn; p is more than 0.61 and less than or equal to 0.78,0.22, x is more than or equal to 0.33,0.10, y is more than or equal to 0.12,0.45, z is more than or equal to 0.78,0.08, q is more than or equal to 0.12, and x+y+z+q=1; alpha is more than 0 and less than or equal to 0.1; beta is more than 0 and less than or equal to 0.05, and the values of p, x, y, z, q, alpha and beta meet the charge balance of chemical formulas.
2. The dianion sodium ion battery positive electrode material of claim 1, wherein M is selected from one or more of Mg, ca, sr, sn, zn, Y, nb, sb, bi, cd, mo, cr and Co.
3. The method for preparing the positive electrode material of the dianion sodium ion battery according to claim 1 or 2, which is characterized by comprising the following steps,
(1) Uniformly mixing a copper source, an iron source, a manganese source and an M source, and performing ball milling and calcination to obtain an M doped precursor;
(2) And (3) uniformly mixing the M doped precursor in the step (1) with a sulfuric acid source, a fluorine source and a sodium source, ball milling and calcining to obtain the dianion sodium ion battery anode material.
4. The method for producing a dianion sodium ion battery positive electrode material according to claim 3, wherein in the step (1), the copper source, the iron source and the manganese source are independently selected from one or more of oxides, carbonates, acetates and hydroxides of the respective elements;
the M source is selected from one or more of oxides, carbonates, fluorides, hydroxides, acetates and sulfates.
5. The method for preparing a positive electrode material for a dianion sodium ion battery according to claim 3, wherein in the step (1), the calcination temperature is 350 to 500 ℃ and the time is 3 to 6 hours.
6. A dianion sodium ion battery positive electrode material according to claim 3, wherein in step (2), the sulfuric acid source is selected from one or more of sodium sulfate, magnesium sulfate, zinc sulfate, aluminum sulfate and calcium sulfate;
the fluorine source is selected from one or more of sodium fluoride, magnesium fluoride, calcium fluoride and aluminum fluoride;
the sodium source is selected from one or more of sodium fluoride, sodium carbonate, sodium hydroxide, sodium oxalate and sodium sulfate.
7. The method for preparing a positive electrode material for a dianion sodium ion battery according to claim 3, wherein in the step (2), the calcination temperature is 950 ℃ to 1050 ℃ for 8h to 12h.
8. A positive electrode of a sodium ion battery, which is characterized by comprising the dianion sodium ion battery positive electrode material according to claim 1 or 2, a conductive agent and a binder in parts by mass; the consumption of the conductive agent is less than or equal to 10wt%; the usage amount of the binder is less than or equal to 10wt%.
9. The positive electrode of sodium ion battery according to claim 8, wherein the conductive agent is selected from one or more of carbon nanotubes, acetylene black, conductive carbon black, conductive graphite, carbon fibers and graphene;
the binder is selected from one or more of polyolefin, fluorine-containing resin, polypropylene resin and rubber.
10. A sodium ion battery comprising the positive electrode of the sodium ion battery of claim 8 or 9.
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